Ah Receptor Agonists in UV-exposed Toluene Solutions of Decabromodiphenyl Ether (decaBDE) and in Soils Contaminated with Polybrominated Diphenyl Ethers (PBDEs) (9 pp)

Goal, Scope and Background The use of polybrominated diphenyl ethers (PBDEs) as flame retardants increases the risk for emissions of other brominated compounds, such as polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). The large homology in structure of PBDD/Fs and mechanism of toxic action, i.e. the capacity to activate the Ah receptor (AhR) pathway, compared to their well-studied chlorinated analogues, justifies a raised concern to study the environmental levels and fate of these compounds. Decabromodiphenyl ether (decaBDE) is the most widely used PBDE today. Studies on photolytic debromination of decaBDE in organic solvents have shown debromination of decaBDE, as well as formation of PBDFs. However, little is known about the transformation mechanisms and there are only scarce data on photoproducts and PBDE transformation in environmentally relevant matrices. In this study, mechanism-specific dioxin bioassays were used to study photolytic formation of AhR agonists in toluene solutions of decaBDE. In addition, the influence of irradiation time and UV-light wavelength on the formation was studied. PBDE congener patterns and presence of PBDD/Fs were analysed. Further, AhR agonists were analysed in agricultural soils contaminated with PBDEs. Soils were also exposed to UV-light to study changes in AhR agonist levels. Methods Toluene solutions of decaBDE were irradiated using three different spectra of UV-light, simulating UV-A (320-400 nm), UV-AB (280-400 nm), and UV-ABC (250-400 nm). Additionally, decaBDE solutions were exposed to narrow wavelength intervals (10 nm bandwidth) with the central wavelengths 280, 290, 300, 310, 320, 330, 340, 350, 360 nm. AhR agonists in decaBDE solutions were analysed with two different bioassays, the chick embryo liver-cell assay for dioxins (Celcad) and the dioxin responsive, chemically activated luciferase expression assay (DR-Calux). Also, the decaBDE solutions were analysed with LRGC-LRMS to obtain PBDE congener patterns for breakdown of decaBDE, and with HRGC-HRMS, for presence of PBDD/Fs. Four soils were exposed to UV-AB light, under both dry and moist conditions. Levels of AhR agonists in soil extract fractions, before and after UV-exposure, were analysed with the DR-Calux. Results and Discussion Significant levels of photoproducts able to activate the AhR pathway, up to 31 ng bio-TEQ/ml, were formed in UV-exposed decaBDE solutions. The transformation yield of decaBDE into AhR agonists was estimated to be at the 0.1%-level, on a molar basis. The net formation was highly dependent on wavelength, with the sample irradiated at 330 nm showing the highest level of dioxin-like activity. No activity was detected in controls. PBDE analysis confirmed decaBDE degradation and a clear time-dependent pattern for debromination of PBDE congeners. AhR agonist effect in the recalcitrant fractions of the soils corresponded to the levels of chemically derived TEQs, based only on chlorinated dioxin-like compounds in an earlier study. It was concluded that no significant levels of other AhR agonists, e.g. PBDFs, were accumulated in the soil. UV-light caused changes in AhR-mediated activity in the more polar and less persistent fractions of the soils, but it is not known which compounds are responsible for this. Recommendations and Perspective . The laboratory experiments in this study show that high levels of AhR agonists can be formed as photoproducts of decaBDE and it is important to elucidate if and under which conditions this might occur in nature. However, soil analysis indicates that photoproducts of PBDE do not contribute to the accumulated levels of persistent dioxin-like compounds in agricultural soil. Still, more data is needed to fully estimate the environmental importance of PBDE photolysis and occurrence of its photoproducts in other environmental compartments. Analysis with dioxin bioassays enabled us to gather information about photoproducts formed from decaBDE even though the exact identities of these compounds were not known. Conclusion Bioassays are valuable for studying environmental transformation processes like this, where chemical analysis and subsequent toxicological evaluation requires available standard compounds and information on toxicological potency. The use of bioassays allows a rapid evaluation of toxicological relevance.     

典型地区大气中多溴联苯醚和新型溴代阻燃剂的水平及组成分布

溴代阻燃剂被广泛应用于工业和商业产品中,广泛存在于各种环境介质中,可能会对环境和人体产生潜在的危害.本研究选取我国溴代阻燃剂生产源区山东省潍坊市滨海开发区为生产源区域,广西壮族自治区南宁市作为对照区域,测定两地大气中8种多溴联苯醚(PBDEs:BDE-28,-47,-100,-99,-154,-153,-183,-209)和新型溴代阻燃剂(NBFRs:PBT,PBEB,HBB)的浓度.结果表明,潍坊和南宁大气中Σ8PBDEs算术平均浓度分别为1.4×105pg·m-3和323.0 pg·m-3,Σ3NBFRs算术平均浓度分别为4.2×103pg·m-3和11.9 pg·m-3.与其他城市相比,生产源区大气中溴代阻燃剂浓度在全球范围内处于较高污染水平,南宁市则与我国其他城市的水平相当,生产源区大气中PBDEs的分布特征异于南宁,PBEB、PBT、HBB及BDE-209之间的相关性在两城市也具有一定的差异.     

废旧电器拆解区河流沉积物中多溴联苯醚(PBDEs)的污染特征与生态风险

在流经某废旧电器拆解区域的河段中采集沉积物样品,研究了该区域河流中多溴联苯醚(PBDEs)的污染特征和生态风险.结果表明,在所有沉积物样品中PBDEs含量在101~20400 ng·g-1之间,平均浓度为3700 ng·g-1,其中主要单体为BDE209,在23个样品中的平均比例达到94%以上;在河流中分布呈现出上游和下游低,中游高,而下游平均浓度比上游高的趋势,在拆解园区附近浓度达到最高;与其它地区相比,该地区PBDEs污染相对较为严重;废旧电器的拆解是该区域沉积物中PBDEs污染主要来源.经测算,当地近40年的拆解活动中共向该河流中排放了多溴联苯醚0.39 t,其中BDE209为0.36 t;采用危害商数法对沉积物中PBDEs进行了初步的生态风险评估,结果表明,该河流沉积物中OctaBDEs和DecaBDEs生态风险较低,而PentaBDEs则风险较高,可能对环境造成危害.     

纳米零价铁还原溴代阻燃剂的进展研究

地表水、地下水和土壤污染是当今社会人类生存面临的主要问题.由于溴代阻燃剂的广泛应用以及它们的难降解性、毒性和蓄积性等特性,成为水体和土壤的严重污染源.纳米零价铁比表面积大、还原性强、价格低廉且毒性小,通过零价铁有效还原转化来降低溴代阻燃剂的毒性是一项有前景的环境修复技术.对纳米零价铁的制备、改性和环境应用进行了介绍,系统探讨了纳米零价铁还原溴代阻燃剂的研究成果和现状,并对其发展前景进行了展望.     

办公楼聚集区空气中PBDEs谱分布与污染特征

为评估办公楼密集区大气中PBDEs污染程度、同类物分布特征及其健康风险,采集了典型科研园区室外空气样品(颗粒物+气态),利用GC-MS对PBDEs质量浓度进行测定.结果表明,PBDEs在气态、PM_(2. 5)和PM_(10)中质量浓度分别为2. 3～78. 6、14. 4～335. 3和11. 6～431. 7 pg·m~(-3),平均值为21. 7、96. 9和149. 3 pg·m~(-3),BDE-209是颗粒态PBDEs中质量浓度最高的同系物,占PBDEs总量的50%.颗粒物中PBDEs质量浓度均表现为秋季冬季夏季春季,冬季变化显著,夏季相对稳定.三溴联苯醚主要存在于气态中,随溴原子的增加,颗粒态PBDEs单体的含量比重增大.来源分析说明BDE-209的降解是空气中其他PBDEs组分的重要来源.暴露风险分析显示儿童和成人对PBDEs的呼吸摄入量分别为18. 6 pg·(kg·d)~(-1)和7. 1 pg·(kg·d)~(-1),远小于相关研究中推荐的最低观察不良反应水平1 mg·(kg·d)~(-1); BDE-209对成人和儿童的致癌风险值分别为3. 7×10-9和2. 3×10-9,远小于致癌风险限值10-6,表明该区域大气中PBDEs无健康危害.     

Effects of nitrogen and phosphorus concentrations on the bioaccumulation of polybrominated diphenyl ethers by Prorocentrum donghaiense

The growth, cellular total lipids, bioaccumulation amount, and bioaccumulation factors (BAFs) of 2,4,4 ′ -tribromodiphenyl ether (BDE28), 2,2 ′ ,4,4 ′ -tetrabromodiphenyl ether (BDE47), and 2,2 ′ ,4,4 ′ ,5-pentabromodiphenyl ether (BDE99) in a semi-continuous culture of Prorocentrum donghaiense were studied in relation to nitrate (0, 128, and 512 μmol/L) and phosphate (0, 8, and 32 μmol/L) concentrations. The BDE28, BDE47, and BDE99 content per cell under 0 μmol N/L were 3.77 × 10 6 , 3.95 × 10 6 , and 4.32 × 10 6 ng/cell, respectively, which were significantly higher than those under 128 and 512 μmol N/L. A nearly 5-fold increase in polybrominated diphenyl ether (PBDE) content per algal cell was found between 0 and 8 μmol P/L and between 8 and 32 μmol P/L. With increasing N and P concentrations, the PBDE content per volume of algal culture and the accumulation percentage of available PBDEs declined slightly. The BAFs for the PBDEs based on lipids showed that the logBAF lip under 0 μmol N/L was higher than those under 128 and 512 μmol N/L. The logBAF lip under 0 μmol P/L was higher than that under 8 μmol P/L but lower than that under 32 μmol P/L. Correlation analysis indicated a significant negative correlation between nutrient concentration and cellular total lipids, as well as the PBDE content per cell. The results indicate that different N and P concentrations change the total lipids content of P. donghaiense, thereby resulting in varying PBDE accumulation.     

中国东北沈抚地区土壤中PBDEs的残留、来源及风险评价

为研究我国东北地区表层土壤中多溴联苯醚(PBDEs)的残留和分布.于2016夏季采集了3个城市(沈阳、抚顺和沈抚新区)的72份土壤样品,覆盖本地区4种不同的土地利用类型:城镇用地,农村居住用地,耕地和林地.分析了表层土壤中14种PBDEs的残留,组成和分布特征,探究了本地区PBDEs主要来源及贡献率,并对人体暴露水平和健康风险进行了评估.结果表明,表层土壤Σ_(14)PBDEs的含量(以干重计,下同)范围在0. 279～50. 719 ng·g~(-1)之间,均值为(10. 466±9. 246) ng·g~(-1).不同城市PBDEs的含量规律为:抚顺沈阳沈抚新区背景点,不同类型土地规律为:城镇用地农村居住用地耕地林地.在所有PBDEs组分中,十溴联苯醚占比最高,为81. 25%～89. 23%.来源分析表明,商用十溴联苯醚是主要来源,多元线性回归分析(PCA-MLR)结果显示其贡献率为66. 06%.暴露水平和健康风险评价的结果又表明,5种不同人群中,抚顺的幼儿人群暴露剂量最高,为(20. 98±25. 01) ng·(kg·d)~(-1)在不同土地类型中,城镇用地的幼儿人群暴露剂量最高,(18. 54±20. 27)ng·(kg·d)~(-1),本地区总体非致癌健康风险处于较低水平.     

Glucuronidation of hydroxylated polybrominated diphenyl ethers and their modulation of estrogen UDP-glucuronosyltransferases

Polybrominated diphenyl ethers (PBDEs) can be metabolically converted to their hydroxylated metabolites (OH-PBDEs). The estrogenic effects of PBDEs may be mediated by OH-PBDEs, but the mechanisms of which are still not understood. This study investigated the glucuronidation of 11 OH-PBDEs and their potential in modulating UDP-glucuronosyltransferases (UGTs) activity of 17β-estradiol (E2) in rat liver microsomes. The number of bromine atoms at phenolic ring was observed as the most influential factor of OH-PBDEs glucuronidation. 2′-OH-BDE-28 having one bromine atom at phenolic ring showed the fastest metabolic rates with t_1/2 value of 3.86 min, while 6-OH-BDE-137 having four bromine atoms at phenolic ring was the poorest substrate with t_1/2 value over 60 min. Regarding to the modulation of E2-UGTs activity, the phenolic hydroxyl group in OH-PBDEs played an essential role. Depending on the substitution patterns of bromine and hydroxyl group, OH-PBDEs inhibited or stimulated E2-UGTs activity. Ten of OH-PBDEs inhibited both 3-glucuronidation and 17-glucuronidation of E2 with IC₅₀ values varying from 3.80 to 129.38 μM, while 3′-OH-BDE-100 exhibited stimulating effects on 3-glucuronidation with EC₅₀ value of 35.95 μM. Kinetic analysis suggested noncompetitive inhibition mode of E2 glucuronidation by 3′-OH-BDE-7, 6-OH-BDE-47 and 2′-OH-BDE-68 with K_i values varying from 11.95 to 67.22 μM. This study demonstrated OH-PBDEs exhibited large interindividual differences in glucuronidation and modulation of E2-UGTs activity. By inhibiting the formation of E2 glucuronidation, OH-PBDEs may increase E2 bioavailability in target tissue, thereby exerting an indirect estrogenic effect.     

MOFs凝胶膜片微固相萃取-气相色谱法测定水样中多溴联苯醚

为实现对环境水样中污染物PBDEs(多溴联苯醚)的预富集和分析,利用溶胶-凝胶法制取了一种MOFs(金属有机骨架材料)凝胶膜片微固相萃取装置,结合GC-ECD(气相色谱-电子捕获检测器)检测方法测定环境水样中的7种PBDEs,考察了MOFs用量、萃取温度、萃取时间和解吸时间对于萃取效果的影响. 结果表明,在MOFs用量为4mg、萃取温度为70℃、萃取时间为50min、解吸时间为15min的条件下,7种PBDEs单体的加标回收率为74.9%~98.1%,相对标准偏差为3.3%~5.7%,方法检出限均小于4.7ng/L.      

多溴二苯醚类化合物干扰人雌激素受体alpha活性机理的理论研究

基于分子对接方法探讨了多溴二苯醚(PBDEs)类化合物与人雌激素受体α亚型间的分子作用机理.对多溴二苯醚类化合物是否具有拟雌激素功能的研究得出:可通过对接打分值和化合物结构特征来推测PBDEs母体化合物是否具有拟雌激素活性;对HO-PBDEs,与氨基酸残基GLU53和/或ARG394形成氢键可能是影响其拟雌激素活性的重要因素;对MeO-PBDEs,疏水MeO-位于结合腔的疏水中部有利于拟雌激素活性.从结构及构象分析得出,邻位疏水基(Br-、MeO-)有利于PBDEs类化合物的拟雌激素活性.同时对多溴二苯醚类化合物是否具有抗雌激素功能的结合特征研究发现,表现出抗雌激素活性的部分PBDEs类化合物伸进通常被雌激素受体拮抗剂雷洛昔芬和4-羟基它莫西芬的烷基胺侧链占据的通道,而大多数未表现出抗雌激素活性的PBDEs类化合物的结合模式类似雌激素受体激动剂17β-雌二醇,位于结合腔,没有伸进通道.本研究从化合物结构及化合物在受体内结合的构象特征上解释化合物活性不同的原因,以期能够利用构象分析得到的结果进行筛选.